JP2024015474A - Method for cleaning semiconductor substrate, method for manufacturing processed semiconductor substrate, and composition for peeling and dissolving - Google Patents

Abstract

To provide, for example, a method for cleaning a semiconductor substrate, in which an adhesive layer can be easily removed (cleaned) in a shorter time and more cleanly from a semiconductor substrate having an adhesive layer on its surface obtained using a siloxane adhesive, a method for manufacturing a processed semiconductor substrate including such a cleaning method, and a composition for use in such a cleaning method.SOLUTION: In a method for cleaning a semiconductor substrate, including a step of peeling and dissolving an adhesive layer on a semiconductor substrate using a peeling and dissolving composition, the peeling and dissolving composition includes a [I] component, a quaternary ammonium salt, a [II] component of an amide solvent, and a [III] component of a solvent represented by a following formula (L). (In the formula, L1 and L2 each independently represent an alkyl group having 2 to 5 carbon atoms, and L3 represents O or S.)SELECTED DRAWING: None

Description

The present invention relates to a method for cleaning a semiconductor substrate, a method for manufacturing a processed semiconductor substrate, and a composition for stripping and dissolving.

Semiconductor wafers have conventionally been integrated in a two-dimensional planar direction, but for the purpose of further integration, there is a need for a semiconductor integration technology in which the planar surfaces are further integrated (stacked) in a three-dimensional direction. This three-dimensional stacking is a technology in which devices are integrated into multiple layers while being connected using through silicon vias (TSV). When integrating multiple layers, each wafer to be integrated is thinned by polishing on the side opposite to the circuit surface on which it is formed (ie, the back surface), and the thinned semiconductor wafers are stacked.

An unthinned semiconductor wafer (also referred to herein simply as a wafer) is bonded to a support for polishing in a polishing device. Since the adhesion at that time must be easily peeled off after polishing, it is called temporary adhesion. This temporary bond must be easily removed from the support, and the thinned semiconductor wafer may be cut or deformed if large forces are applied during removal, and measures must be taken to prevent this from occurring. can be easily removed. However, it is undesirable that the backside of the semiconductor wafer be removed or shifted due to polishing stress during backside polishing of the semiconductor wafer. Therefore, the performance required for temporary bonding is that it can withstand stress during polishing and be easily removed after polishing. For example, performance is required to have high stress (strong adhesive force) in the planar direction during polishing and low stress (weak adhesive force) in the direction crossing the planar direction, ie, the vertical direction, during removal. In addition, heat resistance is also required, as temperatures may reach temperatures of 150° C. or higher during the processing process.

Under these circumstances, in the semiconductor field, polysiloxane adhesives that can have these properties are mainly used as temporary adhesives. In polysiloxane bonding using polysiloxane adhesives, adhesive residue often remains on the substrate surface after the thinned substrate is peeled off, but in order to avoid problems in subsequent processes, In addition, cleaning compositions for removing this residue and cleaning the surface of semiconductor substrates have been developed (see, for example, Patent Documents 1 and 2). Patent Document 1 discloses a siloxane resin remover containing a polar aprotic solvent and quaternary ammonium hydroxide, and Patent Document 2 discloses a cured resin remover containing alkyl ammonium fluoride. has been done. However, in the recent semiconductor field, there is always a demand for new cleaning compositions, and there is always a demand for effective cleaning compositions and cleaning methods.

International Publication No. 2014/092022 US Patent No. 6,818,608

The cleaning compositions described in Patent Documents 1 and 2 above attempt to remove adhesive residue from the substrate surface by dissolving the adhesive residue on the substrate surface. Attempts to remove adhesive residues from substrate surfaces have been found to take a long time to remove.

By the way, as a result of studying cleaning compositions, the present inventors found that when a composition containing a specific component is used, the adhesive layer can be swollen and the adhesive layer can be peeled off from the substrate. By using a composition containing this specific component, the adhesive layer can be removed from the substrate in a short time.
However, there is room for improvement from the perspective of removing adhesive residue from the substrate surface more cleanly in a shorter time with a simple operation, and in search of a more effective cleaning method, a new cleaning method The development of compositions for use in cleaning methods and cleaning methods is progressing.

The present invention has been developed in view of the above circumstances, and can be easily removed (cleaned) from a semiconductor substrate having an adhesive layer obtained using a siloxane adhesive on its surface in a shorter time and more cleanly. ), a method for manufacturing a processed semiconductor substrate including such a cleaning method, and a composition for use in such a cleaning method.

As a result of intensive studies to solve the above problems, the present inventors have found that adhesive layers on semiconductor substrates can be made from siloxane-based adhesives containing a polyorganosiloxane component (A') that hardens through a hydrosilylation reaction. By cleaning the resulting cured adhesive layer using a composition containing specific components, the adhesive layer is swollen and peeled and dissolved in one cleaning operation. The inventors have discovered that the above problems can be solved by removing the adhesive layer from the semiconductor substrate, and have completed the present invention.

（式中、Ｌ^１及びＬ^２は、それぞれ独立して、炭素数２～５のアルキル基を表し、Ｌ^３は、Ｏ又はＳを表す。）
[２]前記剥離及び溶解用組成物が、さらに[ＩＶ]成分：下記式（Ｔ）または下記式（Ｇ）で表される溶媒を含む、[１]に記載の半導体基板の洗浄方法。
（式中、Ｘ^１及びＸ^３は、それぞれ独立して、アルキル基、またはアシル基（Ｘ^４－Ｃ（＝Ｏ）－）を表し、Ｘ^２は、アルキレン基を表し、ｎは、２または３を表す。Ｘ^４は、アルキル基を表す。）
（式中、Ｌ^1１及びＬ^１２は、それぞれ独立して、炭素数１～６のアルキル基を表し、Ｌ^1１のアルキル基の炭素数とＬ^１２のアルキル基の炭素数の合計は、７以下である。）
[３]前記第四級アンモニウム塩が、含ハロゲン第四級アンモニウム塩である、[１]または[２]に記載の半導体基板の洗浄方法。
[４]前記アミド系溶媒が、下記式（Ｚ）で表される酸アミド誘導体、または下記式（Ｙ）で表される化合物である、[１]～[３]のいずれかに記載の半導体基板の洗浄方法。

（式中、Ｒ^０は、エチル基、プロピル基又はイソプロピル基を表し、Ｒ^Ａ及びＲ^Ｂは、それぞれ独立して、炭素数１～４のアルキル基を表す。）

（式中、Ｒ^１０１は水素原子又は炭素数１～６のアルキル基を表し、Ｒ^１０２は炭素数１～６のアルキレン基又は下記式（Ｙ１）で表される基を表す。）
（式中、Ｒ^１０３は水素原子又は炭素数１～６のアルキル基を表し、Ｒ^１０４は炭素数１～５のアルキレン基を表し、＊１は式（Ｙ）中の炭素原子に結合する結合手を表し、＊２は式（Ｙ）中の窒素原子に結合する結合手を表す。）
[５]前記Ｌ¹及びＬ^２が、同一の基である、[１]～[４]のいずれかに記載の半導体基板の洗浄方法。
[６]前記接着層が、シロキサン系接着剤、アクリル樹脂系接着剤、エポキシ樹脂系接着剤、ポリアミド系接着剤、ポリスチレン系接着剤、ポリイミド接着剤及びフェノール樹脂系接着剤から選ばれる少なくとも１種を含む接着剤成分（Ｓ）を含む接着剤組成物を用いて得られる膜である、[１]～[５]のいずれかに記載の半導体基板の洗浄方法。
[７]前記接着剤成分（Ｓ）が、シロキサン系接着剤を含む、[６]に記載の半導体基板の洗浄方法。
[８]前記シロキサン系接着剤が、ヒドロシリル化反応により硬化するポリオルガノシロキサン成分（Ａ’）を含む、[７]に記載の半導体基板の洗浄方法。
[９]前記剥離及び溶解する工程が、剥離された接着層を取り除く工程を含む、[１]～[８]のいずれかに記載の半導体基板の洗浄方法。
[１０]半導体基板と、支持基板と、接着剤組成物から得られる接着層とを備える積層体を製造する第１工程、
得られた積層体の半導体基板を加工する第２工程、
支持基板から、半導体基板及び接着層を分離する第３工程、及び
半導体基板上の接着層を剥離及び溶解用組成物を用いて剥離及び溶解して除去する第４工程
を含む、加工された半導体基板の製造方法において、
前記剥離及び溶解用組成物が、
[Ｉ]成分：第四級アンモニウム塩、
[ＩＩ]成分：アミド系溶媒、及び
[ＩＩＩ]成分：下記式（Ｌ）で表される溶媒
を含むことを特徴とする加工された半導体基板の製造方法。

（式中、Ｌ^１及びＬ^２は、それぞれ独立して、炭素数２～５のアルキル基を表し、Ｌ^３は、Ｏ又はＳを表す。）
[１１]前記剥離及び溶解用組成物が、さらに[ＩＶ]成分：下記式（Ｔ）または下記式（Ｇ）で表される溶媒を含む、[１０]に記載の加工された半導体基板の製造方法。
（式中、Ｘ^１及びＸ^３は、それぞれ独立して、アルキル基、またはアシル基（Ｘ^４－Ｃ（＝Ｏ）－）を表し、Ｘ^２は、アルキレン基を表し、ｎは、２または３を表す。Ｘ^４は、アルキル基を表す。）
（式中、Ｌ^1１及びＬ^１２は、それぞれ独立して、炭素数１～６のアルキル基を表し、Ｌ^1１のアルキル基の炭素数とＬ^１２のアルキル基の炭素数の合計は、７以下である。）
[１２]前記第四級アンモニウム塩が、含ハロゲン第四級アンモニウム塩である、[１０]または[１１]に記載の加工された半導体基板の製造方法。
[１３]前記アミド系溶媒が、下記式（Ｚ）で表される酸アミド誘導体、または下記式（Ｙ）で表される化合物である、[１０]～[１２]のいずれかに記載の加工された半導体基板の製造方法。

（式中、Ｒ^０は、エチル基、プロピル基又はイソプロピル基を表し、Ｒ^Ａ及びＲ^Ｂは、それぞれ独立して、炭素数１～４のアルキル基を表す。）

（式中、Ｒ^１０１は水素原子又は炭素数１～６のアルキル基を表し、Ｒ^１０２は炭素数１～６のアルキレン基又は下記式（Ｙ１）で表される基を表す。）
（式中、Ｒ^１０３は水素原子又は炭素数１～６のアルキル基を表し、Ｒ^１０４は炭素数１～５のアルキレン基を表し、＊１は式（Ｙ）中の炭素原子に結合する結合手を表し、＊２は式（Ｙ）中の窒素原子に結合する結合手を表す。）
[１４]前記Ｌ¹及びＬ^２が、同一の基である、[１０]～[１３]のいずれかに記載の加工された半導体基板の製造方法。
[１５]前記接着層が、シロキサン系接着剤、アクリル樹脂系接着剤、エポキシ樹脂系接着剤、ポリアミド系接着剤、ポリスチレン系接着剤、ポリイミド接着剤及びフェノール樹脂系接着剤から選ばれる少なくとも１種を含む接着剤成分（Ｓ）を含む接着剤組成物を用いて得られる膜である、[１０]～[１４]のいずれかに記載の加工された半導体基板の製造方法。
[１６]前記接着剤成分（Ｓ）が、シロキサン系接着剤を含む、[１５]に記載の加工された半導体基板の製造方法。
[１７]前記シロキサン系接着剤が、ヒドロシリル化反応により硬化するポリオルガノシロキサン成分（Ａ’）を含む、[１６]に記載の加工された半導体基板の製造方法。
[１８]前記剥離及び溶解して除去する第４工程が、剥離された接着層を取り除く工程を含む、[１０]～[１７]のいずれかに記載の加工された半導体基板の製造方法。
[１９]半導体基板を洗浄する際に前記半導体基板上の接着層を剥離及び溶解して除去するために用いられる剥離及び溶解用組成物であって、
前記剥離及び溶解用組成物が、
[Ｉ]成分：第四級アンモニウム塩、
[ＩＩ]成分：アミド系溶媒、及び
[ＩＩＩ]成分：下記式（Ｌ）で表される溶媒
を含み、
前記剥離及び溶解用組成物中、非プロトン性溶媒１００質量％における前記[ＩＩＩ]成分の含有量が３０質量％以上であることを特徴とする剥離及び溶解用組成物。

（式中、Ｌ^１及びＬ^２は、それぞれ独立して、炭素数２～５のアルキル基を表し、Ｌ^３は、Ｏ又はＳを表す。）
[２０]前記剥離及び溶解用組成物が、さらに[ＩＶ]成分：下記式（Ｔ）または下記式（Ｇ）で表される溶媒を含む、[１９]に記載の剥離及び溶解用組成物。
（式中、Ｘ^１及びＸ^３は、それぞれ独立して、アルキル基、またはアシル基（Ｘ^４－Ｃ（＝Ｏ）－）を表し、Ｘ^２は、アルキレン基を表し、ｎは、２または３を表す。Ｘ^４は、アルキル基を表す。）
（式中、Ｌ^1１及びＬ^１２は、それぞれ独立して、炭素数１～６のアルキル基を表し、Ｌ^1１のアルキル基の炭素数とＬ^１２のアルキル基の炭素数の合計は、７以下である。）
[２１]前記第四級アンモニウム塩が、含ハロゲン第四級アンモニウム塩である、[１９]または[２０]に記載の剥離及び溶解用組成物。
[２２]前記アミド系溶媒が、下記式（Ｚ）で表される酸アミド誘導体、または下記式（Ｙ）で表される化合物である、[１９]～[２１]のいずれかに記載の剥離及び溶解用組成物。

（式中、Ｒ^０は、エチル基、プロピル基又はイソプロピル基を表し、Ｒ^Ａ及びＲ^Ｂは、それぞれ独立して、炭素数１～４のアルキル基を表す。）

（式中、Ｒ^１０１は水素原子又は炭素数１～６のアルキル基を表し、Ｒ^１０２は炭素数１～６のアルキレン基又は下記式（Ｙ１）で表される基を表す。）
（式中、Ｒ^１０３は水素原子又は炭素数１～６のアルキル基を表し、Ｒ^１０４は炭素数１～５のアルキレン基を表し、＊１は式（Ｙ）中の炭素原子に結合する結合手を表し、＊２は式（Ｙ）中の窒素原子に結合する結合手を表す。）
[２３]前記Ｌ¹及びＬ^２が、同一の基である、[１９]～[２２]のいずれかに記載の剥離及び溶解用組成物。
[２４]前記接着層が、シロキサン系接着剤、アクリル樹脂系接着剤、エポキシ樹脂系接着剤、ポリアミド系接着剤、ポリスチレン系接着剤、ポリイミド接着剤及びフェノール樹脂系接着剤から選ばれる少なくとも１種を含む接着剤成分（Ｓ）を含む接着剤組成物を用いて得られる膜である、[１９]～[２３]のいずれかに記載の剥離及び溶解用組成物。
[２５]前記接着剤成分（Ｓ）が、シロキサン系接着剤を含む、[２４]に記載の加工された剥離及び溶解用組成物。
[２６]前記シロキサン系接着剤が、ヒドロシリル化反応により硬化するポリオルガノシロキサン成分（Ａ’）を含む、[２５]に記載の剥離及び溶解用組成物。 That is, the present invention includes the following aspects.
[1] A method for cleaning a semiconductor substrate, comprising a step of peeling and dissolving an adhesive layer on the semiconductor substrate using a peeling and dissolving composition,
The stripping and dissolving composition is
[I] Component: quaternary ammonium salt,
[II] Component: amide solvent, and
[III] Component: A method for cleaning a semiconductor substrate, comprising a solvent represented by the following formula (L).

(In the formula, L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.)
[2] The method for cleaning a semiconductor substrate according to [1], wherein the stripping and dissolving composition further contains component [IV]: a solvent represented by the following formula (T) or the following formula (G).
(In the formula, X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is 2 or 3. X ⁴ represents an alkyl group.)
(In the formula, L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is 7 or less. )
[3] The method for cleaning a semiconductor substrate according to [1] or [2], wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.
[4] The semiconductor according to any one of [1] to [3], wherein the amide solvent is an acid amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y). How to clean the board.

(In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, and R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms.)

(In the formula, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰² represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)
(In the formula, R ¹⁰³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁰⁴ represents an alkylene group having 1 to 5 carbon atoms, and *1 is a bond bonded to the carbon atom in formula (Y). *2 represents the bond bonded to the nitrogen atom in formula (Y).)
[5] The method for cleaning a semiconductor substrate according to any one of [1] to [4], wherein L ¹ and L ² are the same group.
[6] The adhesive layer is at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. The method for cleaning a semiconductor substrate according to any one of [1] to [5], wherein the film is obtained using an adhesive composition containing an adhesive component (S).
[7] The method for cleaning a semiconductor substrate according to [6], wherein the adhesive component (S) includes a siloxane adhesive.
[8] The method for cleaning a semiconductor substrate according to [7], wherein the siloxane adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.
[9] The method for cleaning a semiconductor substrate according to any one of [1] to [8], wherein the peeling and dissolving step includes a step of removing the peeled adhesive layer.
[10] A first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition;
a second step of processing the semiconductor substrate of the obtained laminate;
A processed semiconductor comprising: a third step of separating the semiconductor substrate and the adhesive layer from the supporting substrate; and a fourth step of removing the adhesive layer on the semiconductor substrate by peeling and dissolving it using a peeling and dissolving composition. In the method for manufacturing a substrate,
The stripping and dissolving composition is
[I] Component: quaternary ammonium salt,
[II] Component: amide solvent, and
[III] Component: A method for producing a processed semiconductor substrate, characterized by containing a solvent represented by the following formula (L).

(In the formula, L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.)
[11] Production of the processed semiconductor substrate according to [10], wherein the stripping and dissolving composition further contains component [IV]: a solvent represented by the following formula (T) or the following formula (G). Method.
(In the formula, X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is 2 or 3. X ⁴ represents an alkyl group.)
(In the formula, L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is 7 or less. )
[12] The method for producing a processed semiconductor substrate according to [10] or [11], wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.
[13] The process according to any one of [10] to [12], wherein the amide solvent is an acid amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y). A method for manufacturing a semiconductor substrate.

(In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, and R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms.)

(In the formula, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰² represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)
(In the formula, R ¹⁰³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁰⁴ represents an alkylene group having 1 to 5 carbon atoms, and *1 is a bond bonded to the carbon atom in formula (Y). *2 represents the bond bonded to the nitrogen atom in formula (Y).)
[14] The method for producing a processed semiconductor substrate according to any one of [10] to [13], wherein L ¹ and L ² are the same group.
[15] The adhesive layer is at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. The method for producing a processed semiconductor substrate according to any one of [10] to [14], which is a film obtained using an adhesive composition containing an adhesive component (S).
[16] The method for manufacturing a processed semiconductor substrate according to [15], wherein the adhesive component (S) includes a siloxane adhesive.
[17] The method for producing a processed semiconductor substrate according to [16], wherein the siloxane adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.
[18] The method for manufacturing a processed semiconductor substrate according to any one of [10] to [17], wherein the fourth step of peeling and dissolving and removing includes a step of removing the peeled adhesive layer.
[19] A peeling and dissolving composition used for peeling and dissolving and removing the adhesive layer on the semiconductor substrate when cleaning the semiconductor substrate, comprising:
The stripping and dissolving composition comprises:
[I] Component: quaternary ammonium salt,
[II] Component: amide solvent, and
[III] Component: Contains a solvent represented by the following formula (L),
A composition for stripping and dissolving, characterized in that the content of the component [III] in the composition for stripping and dissolving is 30% by mass or more based on 100% by mass of the aprotic solvent.

(In the formula, L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.)
[20] The stripping and dissolving composition according to [19], further comprising component [IV]: a solvent represented by the following formula (T) or the following formula (G).
(In the formula, X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is 2 or 3. X ⁴ represents an alkyl group.)
(In the formula, L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is 7 or less. )
[21] The stripping and dissolving composition according to [19] or [20], wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt.
[22] The peeling according to any one of [19] to [21], wherein the amide solvent is an acid amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y). and a dissolving composition.

(In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, and R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms.)

(In the formula, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰² represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)
(In the formula, R ¹⁰³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁰⁴ represents an alkylene group having 1 to 5 carbon atoms, and *1 is a bond bonded to the carbon atom in formula (Y). *2 represents the bond bonded to the nitrogen atom in formula (Y).)
[23] The peeling and dissolving composition according to any one of [19] to [22], wherein L ¹ and L ² are the same group.
[24] The adhesive layer is at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. The peeling and dissolving composition according to any one of [19] to [23], which is a film obtained using an adhesive composition containing an adhesive component (S).
[25] The processed peeling and dissolving composition according to [24], wherein the adhesive component (S) includes a siloxane adhesive.
[26] The peeling and dissolving composition according to [25], wherein the siloxane adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.

ADVANTAGE OF THE INVENTION According to the present invention, a method for cleaning a semiconductor substrate, which can remove (clean) a semiconductor substrate having an adhesive layer on its surface with a simple operation, in a shorter time, and more cleanly, includes such a cleaning method. A method for manufacturing a processed semiconductor substrate and a composition for use in such a cleaning method can be provided.

The present invention will be explained in detail below. Note that the explanation of the constituent elements described below is an illustration for explaining the present invention, and the present invention is not limited to these contents.

(Cleaning method for semiconductor substrate)
The method for cleaning a semiconductor substrate of the present invention includes a step of peeling and dissolving an adhesive layer on a semiconductor substrate using a peeling and dissolving composition.
The stripping and dissolving composition is
[I] Component: quaternary ammonium salt,
[II] Component: amide solvent, and
[III] Component: Contains a solvent represented by the following formula (L).

（式中、Ｌ^１及びＬ^２は、それぞれ独立して、炭素数２～５のアルキル基を表し、Ｌ^３は、Ｏ又はＳを表す。）

(In the formula, L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.)

The stripping and dissolving composition further comprises:
[IV] Component: May contain a solvent represented by the following formula (T) or the following formula (G).

(In the formula, X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is 2 or 3. X ⁴ represents an alkyl group.)

(In the formula, L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is 7 or less. )

<Semiconductor substrate>
The main material constituting the entire semiconductor substrate is not particularly limited as long as it is used for this type of application, and examples thereof include silicon, silicon carbide, and compound semiconductors.
The shape of the semiconductor substrate is not particularly limited, but is, for example, disc-shaped. Note that the surface of a disk-shaped semiconductor substrate does not need to have a completely circular shape; for example, the outer periphery of the semiconductor substrate may have a straight part called an orientation flat, or a straight part called a notch. It may have a notch.
The thickness of the disk-shaped semiconductor substrate may be determined as appropriate depending on the intended use of the semiconductor substrate, and is, for example, 500 to 1,000 μm, although it is not particularly limited.
The diameter of the disk-shaped semiconductor substrate may be determined as appropriate depending on the intended use of the semiconductor substrate, and is not particularly limited, but may be, for example, 100 to 1,000 mm.

The semiconductor substrate is, for example, a wafer, and a specific example thereof includes a silicon wafer with a diameter of about 300 mm and a thickness of about 770 μm, but is not limited thereto.

<Adhesive layer>
The adhesive layer on the semiconductor substrate is, for example, a film obtained from an adhesive composition containing an adhesive component (S).
Such adhesive component (S) is not particularly limited as long as it is used for this type of application, and examples include siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, and polyamide adhesives. adhesives, polystyrene adhesives, polyimide adhesives, phenolic resin adhesives, and the like.
Among these, siloxane-based adhesives are preferred as the adhesive component (S) because they exhibit suitable adhesion when processing wafers, etc., can be peeled off after processing, and have excellent heat resistance. is preferred.

<<Adhesive composition>>
In a preferred embodiment, the adhesive composition used in the present invention contains, as an adhesive component, a component (A) that is cured by a hydrosilylation reaction.
In a preferred embodiment, the adhesive composition used in the present invention contains polyorganosiloxane.
Component (A) may be a component that hardens through a hydrosilylation reaction, or may be a polyorganosiloxane component (A') that hardens through a hydrosilylation reaction.
In another preferred embodiment, component (A) includes, for example, a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to a silicon atom, as an example of component (A'), and Si- It contains a polyorganosiloxane (a2) having an H group and a platinum group metal catalyst (A2). Here, the alkenyl group having 2 to 40 carbon atoms may be substituted. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.
In another preferred embodiment, the polyorganosiloxane component (A') that is cured by a hydrosilylation reaction has siloxane units (Q units) represented by SiO ₂ , R ¹ R ² R ³ SiO _1/2 One type selected from the group consisting of a siloxane unit (M unit), a siloxane unit (D unit) represented by R ⁴ R ⁵ SiO _2/2 , and a siloxane unit (T unit) represented by R ⁶ SiO _3/2 Or a polysiloxane (A1) containing two or more types of units and a platinum group metal catalyst (A2), wherein the polysiloxane (A1) is a siloxane unit (Q' unit) represented by _SiO2 , ^R1 'R ² 'R ³ 'SiO _1/2 siloxane unit (M' unit), R ⁴ 'R ⁵ 'SiO _2/2 siloxane unit (D' unit) and R ⁶ 'SiO ₃ Contains one or more units selected from the group consisting of siloxane units (T' units) represented by _/2 , and at least one unit selected from the group consisting of M' units, D' units, and T' units. Polyorganosiloxane (a1') containing seeds, siloxane units represented by SiO ₂ (Q" units), siloxane units represented by R ¹ "R ² "R ³ "SiO _1/2 (M" units) , one selected from the group consisting of siloxane units (D" units) represented by R ⁴ "R ⁵ "SiO _2/2 and siloxane units (T" units) represented by R ⁶ "SiO _3/2 , or The polyorganosiloxane (a2') contains two or more types of units and also contains at least one type selected from the group consisting of M" units, D" units, and T" units.
Note that (a1') is an example of (a1), and (a2') is an example of (a2).

R ¹ to R ⁶ are groups or atoms bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

R ¹ ′ to R ⁶ ′ are groups bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or an optionally substituted alkenyl group, but R ¹ ′ to R ⁶ At least one of ' is an optionally substituted alkenyl group. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

R ¹ ” to R ⁶ ” are groups or atoms bonded to a silicon atom, and each independently represents an optionally substituted alkyl group or a hydrogen atom, but at least one of R ¹ ” to R ⁶ ” One is a hydrogen atom. Examples of the substituent include a halogen atom, a nitro group, a cyano group, an amino group, a hydroxy group, a carboxyl group, an aryl group, and a heteroaryl group.

The alkyl group may be linear, branched, or cyclic, but a linear or branched alkyl group is preferable, and the number of carbon atoms thereof is not particularly limited, but is usually 1 to 40. It is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less.

Specific examples of optionally substituted linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group. group, tertiary butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n -pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl- n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl -n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2 Examples include, but are not limited to, -methyl-n-propyl group, and the number of carbon atoms thereof is usually 1 to 14, preferably 1 to 10, and more preferably 1 to 6. Among these, methyl group is particularly preferred.

Specific examples of the optionally substituted cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, and a 2-methyl-cyclopropyl group. Methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group , 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n -propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1 , 2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl Cycloalkyl groups such as -2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, Examples include, but are not limited to, bicycloalkyl groups such as bicyclodecyl groups, and the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.

The alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more Preferably it is 10 or less.

Specific examples of linear or branched alkenyl groups that may be substituted include, but are not limited to, vinyl groups, allyl groups, butenyl groups, pentenyl groups, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, more preferably 1 to 6. Among these, ethenyl group and 2-propenyl group are particularly preferred.
Specific examples of the optionally substituted cyclic alkenyl group include, but are not limited to, cyclopentenyl, cyclohexenyl, etc., and the number of carbon atoms thereof is usually 4 to 14, preferably 5 to 10, More preferably 5 to 6.

As mentioned above, polysiloxane (A1) contains polyorganosiloxane (a1') and polyorganosiloxane (a2'), but the alkenyl group contained in polyorganosiloxane (a1') and polyorganosiloxane (a2' ) and the hydrogen atoms (Si—H group) contained in the compound form a crosslinked structure through a hydrosilylation reaction using a platinum group metal catalyst (A2) and are cured. As a result, a cured film is formed.

The polyorganosiloxane (a1') contains one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, as well as M' units, D' units, and It contains at least one type selected from the group consisting of T' units. As the polyorganosiloxane (a1'), a combination of two or more polyorganosiloxanes that satisfy such conditions may be used.

Preferred combinations of two or more selected from the group consisting of Q' units, M' units, D' units and T' units include (Q' units and M' units), (D' units and M' units), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but are not limited to these.

In addition, when the polyorganosiloxane (a1') contains two or more types of polyorganosiloxanes, a combination of (Q' unit and M' unit) and (D' unit and M' unit), (T' Combinations of (unit and M' unit) and (D' unit and M' unit), combinations of (Q' unit, T' unit and M' unit) and (T' unit and M' unit) are preferred, Not limited to these.

The polyorganosiloxane (a2') contains one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and also contains M" units, D" units, and It contains at least one type selected from the group consisting of T'' units.As the polyorganosiloxane (a2'), two or more types of polyorganosiloxanes satisfying such conditions may be used in combination.

Preferred combinations of two or more selected from the group consisting of Q" units, M" units, D" units, and T" units include (M" units and D" units), (Q" units and M" units), (Q" units, T" units, and M" units), but are not limited to these.

Polyorganosiloxane (a1') is composed of siloxane units in which an alkyl group and/or an alkenyl group are bonded to the silicon atom, and in all substituents represented by R ¹ ' to R ⁶ ', The proportion of alkenyl groups is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, and the remaining R ¹ ′ to R ⁶ ′ can be an alkyl group. .

Polyorganosiloxane (a2') is composed of siloxane units in which an alkyl group and/or a hydrogen atom are bonded to a silicon atom, and all substituents represented by R ¹ '' to R ⁶ '' and The proportion of hydrogen atoms in the substituent atoms is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, and the remaining R ¹ '' to R ⁶ '' are alkyl groups. can do.

When component (A) contains (a1) and (a2), in a preferred embodiment of the present invention, the alkenyl group contained in the polyorganosiloxane (a1) and the Si-H bond contained in the polyorganosiloxane (a2) The molar ratio of hydrogen atoms to hydrogen atoms is in the range of 1.0:0.5 to 1.0:0.66.

The weight average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but each is usually 500 to 1,000,000, and the effects of the present invention can be achieved with good reproducibility. From the viewpoint of this, it is preferably 5,000 to 50,000.
In the present invention, the weight average molecular weight, number average molecular weight, and dispersity of the polyorganosiloxane are measured using, for example, a GPC apparatus (EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation) and a GPC column (TSKgel SuperMultipore HZ-N manufactured by Tosoh Corporation). , TSKgel SuperMultiporeHZ-H), the column temperature was 40°C, tetrahydrofuran was used as the eluent (elution solvent), the flow rate was 0.35 mL/min, and polystyrene (Showa Denko K.K.) was used as the standard sample. , Shodex).

The viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, but each is usually 10 to 1,000,000 (mPa·s), and is preferably from the viewpoint of achieving the effects of the present invention with good reproducibility. is 50 to 20000 (mPa·s). In addition, the viscosity of polyorganosiloxane (a1) and polyorganosiloxane (a2) is a value measured with an E-type rotational viscometer at 25°C.

The polyorganosiloxane (a1) and the polyorganosiloxane (a2) react with each other to form a film through a hydrosilylation reaction. Therefore, the mechanism of curing is different from that via, for example, silanol groups, and therefore it is not necessary for any siloxane to contain silanol groups or functional groups that form silanol groups by hydrolysis, such as alkyloxy groups. None.

In a preferred embodiment of the present invention, the adhesive composition contains a platinum group metal catalyst (A2) together with the polyorganosiloxane component (A').
Such a platinum-based metal catalyst is a catalyst for promoting the hydrosilylation reaction between the alkenyl group of the polyorganosiloxane (a1) and the Si--H group of the polyorganosiloxane (a2).

Specific examples of platinum-based metal catalysts include platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Examples include, but are not limited to, platinum-based catalysts.
Examples of complexes of platinum and olefins include, but are not limited to, complexes of divinyltetramethyldisiloxane and platinum.
The amount of platinum group metal catalyst (A2) is not particularly limited, but is usually in the range of 1.0 to 50.0 ppm based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2). .

The polyorganosiloxane component (A') may contain a polymerization inhibitor (A3) for the purpose of suppressing the progress of the hydrosilylation reaction.
The polymerization inhibitor is not particularly limited as long as it can inhibit the progress of the hydrosilylation reaction, and specific examples thereof include 1-ethynyl-1-cyclohexanol and 1,1-diphenyl-2-propion-1-ol. and other alkynyl alcohols.
The amount of the polymerization inhibitor is not particularly limited, but it is usually 1000.0 ppm or more based on the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2) from the viewpoint of obtaining the effect, and it is necessary to prevent the hydrosilylation reaction. The content is 10,000.0 ppm or less from the viewpoint of preventing excessive suppression of

The adhesive composition used in the present invention may contain a release agent component (B). By including such a release agent component (B) in the adhesive composition used in the present invention, the resulting adhesive layer can be suitably removed with good reproducibility.
Such a release agent component (B) typically includes polyorganosiloxane. In a certain preferred embodiment, specific examples thereof include, but are not limited to, epoxy group-containing polyorganosiloxane, methyl group-containing polyorganosiloxane, phenyl group-containing polyorganosiloxane, and the like.
In another preferred embodiment, the release agent component (B) includes polydimethylsiloxane, and the polydimethylsiloxane may be modified. Examples of the polydimethylsiloxane that may be modified include, but are not limited to, epoxy group-containing polydimethylsiloxane, unmodified polydimethylsiloxane, and phenyl group-containing polydimethylsiloxane.

The weight average molecular weight of the polyorganosiloxane that is the release agent component (B) is not particularly limited, but is usually 100,000 to 2,000,000, and from the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, more preferably 300,000 to 900,000. Further, the degree of dispersion is not particularly limited, but is usually 1.0 to 10.0, preferably 1.5 to 5.0, more preferably 2 from the viewpoint of realizing suitable peeling with good reproducibility. .0 to 3.0. Note that the weight average molecular weight and the degree of dispersion can be measured by the method described above regarding polysiloxane.
The complex viscosity of the polyorganosiloxane, which is the release agent component (B), can be measured at 25° C. using a rheometer (for example, rheometer MCR-302 manufactured by Anton Paar).

Examples of the epoxy group-containing polyorganosiloxane include those containing a siloxane unit (D ¹⁰ unit) represented by R ¹¹ R ¹² SiO _2/2 .

R ¹¹ is a group bonded to a silicon atom and represents an alkyl group; R ¹² is a group bonded to a silicon atom and represents an epoxy group or an organic group containing an epoxy group; specific examples of the alkyl group are , the above-mentioned examples can be cited.
The epoxy group in an organic group containing an epoxy group may be an independent epoxy group without being fused with other rings, or may form a fused ring with other rings, such as a 1,2-epoxycyclohexyl group. It may also be an epoxy group.
Specific examples of organic groups containing epoxy groups include, but are not limited to, 3-glycidoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl.
In the present invention, a preferred example of the epoxy group-containing polyorganosiloxane includes, but is not limited to, epoxy group-containing polydimethylsiloxane.

The epoxy group-containing polyorganosiloxane contains the above-mentioned siloxane unit ( ^D10 unit), but may also contain Q unit, M unit and/or T unit in addition to ^D10 unit.
In a preferred embodiment of the present invention, specific examples of the epoxy group-containing polyorganosiloxane include polyorganosiloxanes containing only D ¹⁰ units, polyorganosiloxanes containing D ¹⁰ units and Q units, and polyorganosiloxanes containing D ¹⁰ units and M units. polyorganosiloxane containing D ¹⁰ units and T units; polyorganosiloxanes containing D ¹⁰ units, Q units and M units; polyorganosiloxanes containing D ¹⁰ units, M units and T units. , a polyorganosiloxane containing ¹⁰ D units, a Q unit, an M unit, and a T unit.

The epoxy group-containing polyorganosiloxane is preferably an epoxy group-containing polydimethylsiloxane having an epoxy value of 0.1 to 5. Further, the weight average molecular weight thereof is not particularly limited, but is usually 1,500 to 500,000, and preferably 100,000 or less from the viewpoint of suppressing precipitation in the adhesive.

Specific examples of the epoxy group-containing polyorganosiloxane include, but are not limited to, those represented by formulas (E1) to (E3).

（ｍ_１及びｎ_１は、各繰り返し単位の数を示し、正の整数である。）

(m ₁ and n ₁ indicate the number of each repeating unit and are positive integers.)

(m ₂ and n ₂ indicate the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

(m ₃ , n ₃ and o ₃ indicate the number of each repeating unit and are positive integers, and R is an alkylene group having 1 to 10 carbon atoms.)

Examples of the methyl group-containing polyorganosiloxane include those containing siloxane units (D ²⁰⁰ units) represented by R ²¹⁰ R ²²⁰ SiO _2/2 , preferably siloxane units represented by R ²¹ R ²¹ SiO _2/2 . ( ^D20 units).

R ²¹⁰ and R ²²⁰ are groups bonded to a silicon atom, and each independently represents an alkyl group, and at least one of them is a methyl group, and specific examples of the alkyl group include the above-mentioned examples. can.
R ²¹ is a group bonded to a silicon atom and represents an alkyl group, and specific examples of the alkyl group include those mentioned above. Among these, R ²¹ is preferably a methyl group.
In the present invention, a preferable example of the methyl group-containing polyorganosiloxane includes polydimethylsiloxane, but is not limited thereto.

The methyl group-containing polyorganosiloxane contains the aforementioned siloxane units (D ²⁰⁰ units or D ²⁰ units), but in addition to the D ²⁰⁰ units and D ²⁰ units, it may also contain Q units, M units, and/or T units. .

In an embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include a polyorganosiloxane containing only D ²⁰⁰ units, a polyorganosiloxane containing D ²⁰⁰ units and Q units, and a polyorganosiloxane containing D ²⁰⁰ units and M units. polyorganosiloxane containing D ²⁰⁰ units and T units; polyorganosiloxanes containing D ²⁰⁰ units, Q units and M units; polyorganosiloxanes containing D ²⁰⁰ units, M units and T units. , ^D200 units, Q units, M units, and T units.

In a preferred embodiment of the present invention, specific examples of the methyl group-containing polyorganosiloxane include polyorganosiloxanes containing only ^D20 units, polyorganosiloxanes containing ^D20 units and Q units, and polyorganosiloxanes containing ^D20 units and M units. polyorganosiloxane containing D ²⁰ units and T units; polyorganosiloxanes containing D ²⁰ units, Q units and M units; polyorganosiloxanes containing D ²⁰ units, M units and T units. , ^D20 units, Q units, M units, and T units.

Specific examples of the methyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (M1).

( _n4 indicates the number of repeating units and is a positive integer.)

Examples of the phenyl group-containing polyorganosiloxane include those containing a siloxane unit (D ³⁰ unit) represented by R ³¹ R ³² SiO _2/2 .

R ³¹ is a group bonded to a silicon atom and represents a phenyl group or an alkyl group, R ³² is a group bonded to a silicon atom and represents a phenyl group, and specific examples of the alkyl group include the above-mentioned examples. can be mentioned, but methyl group is preferred.

The phenyl group-containing polyorganosiloxane contains the above-mentioned siloxane unit ( ^D30 unit), but may also contain Q unit, M unit and/or T unit in addition to ^D30 unit.

In a preferred embodiment of the present invention, specific examples of the phenyl group-containing polyorganosiloxane include polyorganosiloxanes containing only D ³⁰ units, polyorganosiloxanes containing D ³⁰ units and Q units, and polyorganosiloxanes containing D ³⁰ units and M units. polyorganosiloxane containing D ³⁰ units and T units; polyorganosiloxanes containing D ³⁰ units, Q units and M units; polyorganosiloxanes containing D ³⁰ units, M units and T units. , ^D30 units, Q units, M units, and T units.

Specific examples of the phenyl group-containing polyorganosiloxane include, but are not limited to, those represented by formula (P1) or (P2).

(m ₅ and n ₅ indicate the number of each repeating unit and are positive integers.)

(m ₆ and n ₆ indicate the number of each repeating unit and are positive integers.)

The polyorganosiloxane that is the release agent component (B) may be a commercially available product or a synthesized product.
Commercially available polyorganosiloxane products include, for example, WACKERSILICONE FLUID AK series (AK50, AK 350, AK 1000, AK 10000, AK 1000000) manufactured by Wacker Chemi, GENIOPLAST GUM, and dimethyl silicone manufactured by Shin-Etsu Chemical Co., Ltd. Oil (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968), cyclic dimethyl silicone oil (KF-995); Gelest epoxy group-containing polyorganosiloxane (Product name CMS-227, ECMS-327), Shin-Etsu Chemical Co., Ltd. Epoxy group-containing polyorganosiloxane (KF-101, KF-1001, KF-1005, X-22-343), Dow Corning epoxy Group-containing polyorganosiloxane (BY16-839); phenyl group-containing polyorganosiloxane (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest, phenyl group-containing polyorganosiloxane manufactured by Shin-Etsu Chemical Co., Ltd. Examples include, but are not limited to, siloxane (KF50-3000CS) and phenyl group-containing polyorganosiloxane (TSF431, TSF433) manufactured by MOMENTIVE.

The adhesive composition used in the present invention contains a release agent component (B) together with the curing component (A), and in a more preferred embodiment, a polyorganosiloxane is included as the release agent component (B).

An example of the adhesive composition used in the present invention can contain a curing component (A) and a release agent component (B) in any ratio. The ratio of the component (A) and the release agent component (B) is a mass ratio [(A):(B)], preferably 99.995:0.005 to 30:70, more preferably 99.9. :0.1 to 75:25.
That is, when a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction is included, the ratio of the component (A') to the release agent component (B) is the mass ratio [(A'):(B)] The ratio is preferably 99.995:0.005 to 30:70, more preferably 99.9:0.1 to 75:25.

The adhesive composition used in the present invention may contain a solvent for the purpose of adjusting viscosity, etc. Specific examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc. but not limited to.

More specifically, the solvent includes hexane, heptane, octane, nonane, decane, undecane, dodecane, isododecane, menthane, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl Examples include, but are not limited to, ketone, 2-octanone, 2-nonanone, 5-nonanone, and the like. Such solvents can be used alone or in combination of two or more.

When the adhesive composition used in the present invention contains a solvent, the content thereof is determined as appropriate by taking into consideration the viscosity of the desired composition, the coating method employed, the thickness of the thin film to be produced, etc. The amount ranges from about 10 to 90% by mass based on the entire composition.

The viscosity of the adhesive composition used in the present invention is not particularly limited, but is usually 500 to 20,000 mPa·s, preferably 1,000 to 5,000 mPa·s at 25°C. The viscosity of the adhesive composition used in the present invention can be adjusted by changing the types of solvents used, their ratios, the concentrations of film constituents, etc., taking into account various factors such as the application method used and desired film thickness. It is.
In the present invention, the membrane constituent component means a component other than the solvent contained in the composition.

An example of the adhesive composition used in the present invention can be produced by mixing component (A), release agent component (B), and, if used, a solvent.
The mixing order is not particularly limited, but as an example of a method that can easily and reproducibly produce a release adhesive composition, for example, component (A) and release agent component (B) are mixed in a solvent. Examples include, but are not limited to, a method of dissolving component (A) and part of component (B) of the release agent in a solvent, dissolving the remainder in a solvent, and mixing the resulting solutions. In addition, when preparing the adhesive composition, heating may be carried out as appropriate within a range where the components do not decompose or change in quality.
In the present invention, in order to remove foreign substances, the solvent, solution, etc. used may be filtered using a filter or the like during the production of the adhesive composition or after all the components are mixed.

The thickness of the adhesive layer is not particularly limited, but from the viewpoint of obtaining a good peeling effect with good reproducibility, it is preferably 10 to 100 μm, more preferably 20 to 50 μm.

<Peeling and dissolving composition>
A stripping and dissolving composition is a composition used in a method of cleaning a semiconductor substrate to remove an adhesive layer from the semiconductor substrate.
The peeling and dissolving composition contains a component for causing the adhesive layer to swell and peeling the adhesive layer from the semiconductor substrate, and a component for dissolving the adhesive layer.
Specifically, the stripping and dissolving composition includes:
[I] Component: quaternary ammonium salt,
[II] Component: amide solvent, and
[III] Component: Contains a solvent represented by the following formula (L).

（式中、Ｌ^１及びＬ^２は、それぞれ独立して、炭素数２～５のアルキル基を表し、Ｌ^３は、Ｏ又はＳを表す。）

(In the formula, L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.)

The stripping and dissolving composition further comprises:
[IV] Component: May contain a solvent represented by the following formula (T) or the following formula (G).

(In the formula, X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is 2 or 3. X ⁴ represents an alkyl group.)

(In the formula, L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is 7 or less. )

<<[I] Component: Quaternary ammonium salt>>
The quaternary ammonium salt is composed of a quaternary ammonium cation and an anion, and is not particularly limited as long as it can be used for this type of use.
Quaternary ammonium salts are effective as components for dissolving adhesive layers.
Such quaternary ammonium cations typically include tetra(hydrocarbon) ammonium cations. On the other hand, anions that form a pair with it include hydroxide ion (OH ^- ); halogen ions such as fluorine ion (F ^- ), chloride ion (Cl ^- ), bromine ion (Br ^- ), and iodine ion (I ^- ). ; tetrafluoroborate ion (BF ₄ ⁻ ); hexafluorophosphate ion (PF ₆ ⁻ ), and the like, but are not limited to these.

The quaternary ammonium salt is preferably a halogen-containing quaternary ammonium salt, more preferably a fluorine-containing quaternary ammonium salt.
In the quaternary ammonium salt, the halogen atom may be contained in the cation or the anion, but is preferably contained in the anion.

In one preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon) ammonium fluoride.
Specific examples of hydrocarbon groups in tetra(hydrocarbon) ammonium fluoride include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, and 6 to 20 carbon atoms. Examples include aryl groups such as
In a more preferred embodiment, the tetra(hydrocarbon) ammonium fluoride comprises tetraalkylammonium fluoride.
Specific examples of tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also referred to as tetrabutylammonium fluoride). Not limited. Among them, tetrabutylammonium fluoride is preferred.

A hydrate of the quaternary ammonium salt such as tetra(hydrocarbon) ammonium fluoride may be used. Further, quaternary ammonium salts such as tetra(hydrocarbon) ammonium fluoride may be used alone or in combination of two or more.
The amount of the quaternary ammonium salt is not particularly limited as long as it dissolves in the solvent contained in the stripping and dissolving composition, but it is better to include a small amount to avoid damage to the dicing tape during the cleaning process described below. This is preferable because it can be effectively prevented. Specifically, for example, the amount is usually 0.1 to 5% by mass based on the composition for peeling and dissolving.

<<[II] Component: Amide solvent >>

The amide solvent is effective as a component for dissolving the quaternary ammonium salt well and obtaining a stripping and dissolving composition with excellent uniformity.
The amide solvent is preferably an N-substituted amide compound having 4 or more carbon atoms and having no active hydrogen on the nitrogen atom.
A suitable example of the amide solvent is an acid amide derivative represented by the following formula (Z).

In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, preferably an ethyl group or an isopropyl group, and more preferably an ethyl group. R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms may be linear, branched, or cyclic, and specifically includes a methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, n-butyl group, and isobutyl group. , s-butyl group, t-butyl group, cyclobutyl group, etc. Among these, R ^A and R ^B are preferably a methyl group or an ethyl group, both are more preferably a methyl group or an ethyl group, and both are even more preferably a methyl group.

The acid amide derivatives represented by formula (Z) include N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyric acid amide, N, Examples include N-diethylbutyric acid amide, N-ethyl-N-methylbutyric acid amide, N,N-dimethylisobutyric acid amide, N,N-diethylisobutyric acid amide, N-ethyl-N-methylisobutyric acid amide, and the like. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyramide are particularly preferred, and N,N-dimethylpropionamide is more preferred.

The acid amide derivative represented by formula (Z) may be synthesized by a substitution reaction between a corresponding carboxylic acid ester and an amine, or a commercially available product may be used.

Other examples of preferable amide solvents include, for example, compounds represented by formula (Y) including lactam compounds and the like.

In formula (Y), R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰² represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).

Specific examples of the alkyl group having 1 to 6 carbon atoms for R ¹⁰² include methyl group, ethyl group, n-propyl group, n-butyl group, etc. Specific examples of the alkylene group having 1 to 6 carbon atoms include , methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc., but are not limited thereto.

In formula (Y1), R ¹⁰³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁰⁴ represents an alkylene group having 1 to 5 carbon atoms, and *1 is bonded to a carbon atom in formula (Y). *2 represents a bond bonded to the nitrogen atom in formula (Y).

Specific examples of the lactam compound represented by formula (Y) include α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which may be used singly or in combination. More than one species can be used in combination.

In a preferred embodiment, the lactam compound represented by formula (Y) contains 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), and in a more preferred embodiment, N-methylpyrrolidone (NMP ) or N-ethylpyrrolidone (NEP), and in an even more preferred embodiment, N-methylpyrrolidone (NMP).
Further, a preferred embodiment of the compound represented by formula (Y) includes, for example, 1,3-dimethyl-2-imidazolidinone.

In component [II], it is more preferable to use an acid amide derivative represented by formula (Z) in consideration of operational constraints based on regulations regarding the use of chemical substances.

The content of the amide solvent in the stripping and dissolving composition can be 70% by mass or less when the aprotic solvent is 100% by mass in the stripping and dissolving composition.
Further, the content of the amide solvent is preferably 10 to 55% by mass, more preferably 20 to 50% by mass, even more preferably 20 to 45% by mass, when the aprotic solvent is 100% by mass. ~40% by weight is particularly preferred.
In the present invention, the content of the solvents to be mixed is defined as a ratio based on 100% by mass of the aprotic solvent, which is a solvent that does not have a hydroxyl group (-OH).
As a result, protic solvents such as water, methanol, and 1-methoxy-2-propanol are not included in the content ratio criteria.
In the present invention, the aprotic solvent refers to, for example, N,N-dimethylpropionamide, dibutyl ether, dipropylene glycol dimethyl ether, butyl acetate, etc., and the mixing ratio can be determined based on the total amount of these solvents. .

<<[III] Component: Solvent represented by formula (L) >>
The solvent represented by the following formula (L) is effective as a component for swelling the adhesive layer and peeling the adhesive layer from the semiconductor substrate.

In the above formula (L), L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.
L ¹ and L ² may be the same group or different groups, but from the viewpoint of availability, it is preferable that they are the same group.

The alkyl group having 2 to 5 carbon atoms may be linear, branched, or cyclic, but from the viewpoint of realizing peeling of the adhesive layer in a short time with good reproducibility, it is preferably linear or branched. It is a branched alkyl group, more preferably a straight chain.

Specific examples of linear or branched alkyl groups include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n- Examples include, but are not limited to, pentyl groups.

Specific examples of the cyclic alkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, and the like.

In order to realize peeling of the adhesive layer in a short time with good reproducibility, the alkyl group having 2 to 5 carbon atoms is preferably an ethyl group, n-propyl group, n-butyl group, or n-pentyl group, and more preferably is an ethyl group, n-propyl group or n-butyl group.

From the viewpoint of realizing peeling of the adhesive layer in a shorter time with good reproducibility and from the viewpoint of easy availability of the compound, it is preferable that L ¹ and L ² are the same group.

From the viewpoint of realizing peeling of the adhesive layer in a short time with good reproducibility and from the viewpoint of easy availability of the compound, di(n-butyl) ether is a preferable example of the organic solvent represented by formula (L). , diethyl ether, di(n-pentyl) ether, di(n-propyl) sulfide and the like.

The content of the solvent represented by formula (L) in the stripping and dissolving composition is 30% by mass or more when the aprotic solvent is 100% by mass in the stripping and dissolving composition. be able to.
The content of the solvent represented by formula (L) in the stripping and dissolving composition is preferably 30% by mass or more when the aprotic solvent is 100% by mass in the stripping and dissolving composition. , more preferably 31% by mass or more, further preferably 40% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less. Any combination of these upper and lower limits may be used. Therefore, the content of the solvent represented by formula (L) is preferably 30 to 90% by mass, and 40 to 80% by mass when the aprotic solvent is 100% by mass in the stripping and dissolving composition. % is more preferable.
In addition, an arbitrary amount of a solvent for component [IV] represented by the following formula (T) or the following formula (G) is contained in the composition for peeling and dissolving, and a solvent for component [III] represented by formula (L) is added. It can be mixed with a solvent, but in that case, the combined content of component [III] and component [IV] is 30 to 90% by mass when the aprotic solvent is 100% by mass. It is preferable.
In addition, when a solvent for the [IV] component represented by the following formula (T) or the following formula (G) is contained in the peeling and dissolving composition, especially when the [IV] component is represented by the formula (G). In addition to the effect of improving the compatibility between the [II] and [III] components by including the [IV] component, it is possible to further enhance the peeling effect of the adhesive, so that the peeling and If the dissolving composition contains 30% by mass or more of the component represented by formula (L), which is component [III], component [I], component [II], component [III], and formula ( A peeling and dissolving composition containing component [IV] represented by G) is a composition that exhibits the effects of the present invention well.

<<[IV] Component: Solvent represented by formula (T) or formula (G) >>
The solvent represented by the following formula (T) or the following formula (G) is an amide-based solvent that is the above-mentioned [II] component in the stripping and dissolving composition containing the quaternary ammonium salt that is the above-mentioned [I] component. It is effective as an adjusting component for increasing the compatibility between the solvent and the solvent represented by the above formula (L), which is the above component [III].

In formula (T), X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is Represents 2 or 3. X ⁴ represents an alkyl group.

Examples of the alkyl group represented by X _{1 and} group, sec-butyl group, t-butyl group, etc.
Examples of the alkylene group represented by X ₂ include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, and a 1,2-propylene group.
Examples of the alkyl group represented by X ₄ include alkyl groups having 1 to 4 carbon atoms, including the same alkyl groups as X ₁ and X ₃ .

Preferred examples of the solvent represented by formula (T) include dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like.

In formula (G), L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is: 7 or less.

In the above formula (G), L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, but the total number of carbon atoms in the alkyl group of L ¹¹ and the number of carbon atoms in the alkyl group of L ¹² is 7 or less. With such a carbon number, the adhesive layer can be peeled off in a short time with good reproducibility.

The alkyl group may be linear, branched, or cyclic, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

Specific examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group. , n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl- n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl -n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1 , 1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group etc., but are not limited to these.

Specific examples of the cyclic alkyl group include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3 -Methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3- Dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group , 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl -cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclo Examples include, but are not limited to, cycloalkyl groups such as propyl and 2-ethyl-3-methyl-cyclopropyl groups.

From the viewpoint of realizing peeling of the adhesive layer in a shorter time with good reproducibility, the above L ¹¹ is preferably a methyl group, and the above L ¹² is preferably a butyl group or a pentyl group.

Preferred examples of the organic solvent represented by formula (G) include butyl acetate, pentyl acetate, etc. from the viewpoint of realizing peeling of the adhesive layer in a short time with good reproducibility and from the viewpoint of easy availability of the compound. Can be mentioned.

The content of the solvent represented by formula (T) or formula (G) in the stripping and dissolving composition is 0 when the aprotic solvent is 100% by mass in the stripping and dissolving composition. The content is preferably from 1 to 60% by weight, more preferably from 5 to 40% by weight, even more preferably from 5 to 35% by weight, even more preferably from 5 to 31% by weight, particularly preferably from 5 to 30% by weight.

In addition, when the peeling and dissolving composition contains the [IV] component represented by the formula (T) or the formula (G), the total content of the [III] component and the [IV] component is: When the aprotic solvent is taken as 100% by mass, it is preferably 30 to 90% by mass as mentioned above, but more specifically, 40 to 90% by mass is more preferred, and even more preferably 45 to 90% by mass. Preferably, 50 to 80% by weight is even more preferred, 55 to 80% by weight is particularly preferred, and 60 to 80% by mass is particularly more preferred.

<<Peeling and dissolving process>>
In the present invention, a peeling and dissolving composition is continuously brought into contact with the adhesive layer on the semiconductor substrate. By performing this washing operation, the adhesive layer is swollen and peeled off, and the adhesive layer is dissolved. Swelling, peeling, and dissolution of the adhesive layer are performed at the same time in a cleaning operation using a single cleaning composition, so that the adhesive layer can be removed from a semiconductor substrate in a shorter time and more cleanly with a simple cleaning operation. Can be removed (washed).
Note that in the present invention, removal (cleaning) refers to the removal of the adhesive layer from the semiconductor substrate, and even when the adhesive layer swells and is peeled off from the semiconductor substrate, the adhesive layer dissolves in a solution and the semiconductor Even when it disappears from the substrate, it is included in "removal (cleaning)".
The method of continuously contacting the adhesive layer on the semiconductor substrate with the stripping and dissolving composition is particularly limited as long as the adhesive layer on the semiconductor substrate is brought into continuous contact with the stripping and dissolving composition over time. However, this temporal continuity includes not only the case in which the adhesive layer is constantly in contact with the peeling and dissolving composition, but also the case in which, for example, after the adhesive layer has been in contact with the organic solvent for a certain period of time, the contact This includes cases in which the contact is stopped once and then the contact is made again, or cases in which this is repeated.In addition, it includes not only cases in which the entire adhesive layer on the semiconductor substrate is in contact with the peeling and dissolving composition, but also cases in which only a portion of the adhesive layer is in contact with the peeling and dissolving composition. This includes cases where the adhesive layer on the semiconductor substrate is in constant contact with the stripping and dissolving composition, but from the perspective of realizing more effective cleaning with good reproducibility, It is preferable that the adhesive layer on the semiconductor substrate is in contact with the peeling and dissolving composition.

Therefore, in a preferred embodiment of the present invention, the adhesive layer on the semiconductor substrate is swollen and dissolved by immersing the adhesive layer in a peeling and dissolving composition to remove or bond the adhesive layer on the semiconductor substrate. The layer is swollen and dissolved by continuously applying a stripping and dissolving composition onto the adhesive layer and removed from the semiconductor substrate.

In order to immerse the adhesive layer on the semiconductor substrate in the composition for peeling and dissolving, for example, the semiconductor substrate with the adhesive layer attached may be immersed in the composition for peeling and dissolving.
The immersion time is the time required for swelling and dissolution of the adhesive layer to occur and for the adhesive layer to peel off from the semiconductor substrate, and is not particularly limited, but from the viewpoint of realizing more effective cleaning with good reproducibility, It is more than seconds, and from the viewpoint of process throughput, it is less than 5 minutes.

When the adhesive layer on the semiconductor substrate is immersed in the peeling and dissolving composition, the semiconductor substrate with the adhesive layer is moved in the peeling and dissolving composition, the peeling and dissolving composition is caused to circulate, and the peeling is performed using ultrasonic waves. The removal (cleaning) of the adhesive layer may be promoted by vibrating the dissolving composition.

In order to move the semiconductor substrate with the adhesive layer attached in the stripping and dissolving composition, for example, a swing cleaning machine, a paddle type cleaning machine, etc. may be used. If such a cleaning machine is used, the adhesive layer will be removed. When the table on which the attached semiconductor substrate is placed moves or rotates up and down or left and right, the adhesive layer on the semiconductor substrate receives relative convection, or the convection generated by the movement or rotation is transferred to the adhesive layer on the semiconductor substrate. This promotes not only the swelling and dissolution of the adhesive layer on the semiconductor substrate, but also the peeling and dissolution of the adhesive layer from the semiconductor substrate.

In order to cause convection of the stripping and dissolving composition, in addition to the above-mentioned oscillating cleaning machine or paddle-type cleaning machine, for example, typically, a semiconductor substrate with an adhesive layer is fixed on a stage etc. A convection cleaning machine that can create a state in which the stripping and dissolving composition around the stripping and dissolving composition is convected by a stirrer may be used.

In order to vibrate the exfoliating and dissolving composition with ultrasonic waves, an ultrasonic cleaner or an ultrasonic probe may be used, and the conditions are usually 20 kHz to 5 MHz.

In order to continuously supply the stripping and dissolving composition onto the adhesive layer on the semiconductor substrate, it is sufficient to continuously apply the stripping and dissolving composition toward the adhesive layer on the semiconductor substrate. For example, if the adhesive layer on the semiconductor substrate is facing upward, for example, from above (including diagonally above) the adhesive layer on the semiconductor substrate, a rod-shaped or mist-like A stripping and dissolving composition, preferably in the form of a rod, is applied onto the adhesive layer on the semiconductor substrate with temporal continuity. The temporal continuity in this case is not limited to the case where the stripping and dissolving composition is constantly supplied onto the adhesive layer on the semiconductor substrate, but also, for example, after the stripping and dissolving composition is supplied for a certain period of time. This also includes cases in which the supply is stopped once and then the supply is restarted or repeated, but from the perspective of achieving more effective cleaning with good reproducibility, the stripping and dissolving composition is applied to the surface of the semiconductor substrate. Preferably it is always applied above the adhesive layer.

When the peeling and dissolving composition is supplied in the form of a rod onto the adhesive layer on the semiconductor substrate, the flow rate is usually 200 to 500 mL/min.

In some embodiments of the present invention, in order to maintain constant contact with the stripping and dissolving composition, the adhesive layer on the semiconductor substrate is exposed to the vapor of the stripping and dissolving composition using, for example, a steam cleaning machine. May be brought into contact.

When the semiconductor cleaning method of the present invention is used, as described above, the swelling, peeling, and dissolution of the adhesive layer are performed at the same time, so that the semiconductor substrate can be cleaned in a shorter time and more cleanly with a simple cleaning operation. The adhesive layer can be removed (cleaned). However, in addition to this effect, when the semiconductor cleaning method of the present invention is used, damage to the dicing tape during the cleaning process can be prevented.
For example, after a semiconductor wafer is polished and thinned, the thinned semiconductor wafer is mounted on a dicing tape, and then the semiconductor wafer and the support are separated (peeled off). After the support is separated (peeled off), the adhesive layer remaining on the semiconductor wafer side is removed from the semiconductor wafer by cleaning with a cleaning composition. At that time, if a cleaning composition of the type that attempts to dissolve and remove adhesive residue, such as the cleaning compositions of Patent Documents 1 and 2 above, is used as the cleaning composition, the surface of the dicing tape will change. However, the dicing tape is damaged (see the results of [Comparative Example 2-1] described in the Examples section below).
However, when a semiconductor substrate with an adhesive layer is cleaned using the peeling and dissolving composition of the present invention, most of the adhesive layer can be peeled off in a short time, and even a small amount of the adhesive layer remaining after peeling can be used for peeling and dissolving. Since it is dissolved by the dissolved components in the composition, the entire removal (cleaning) time for removing the adhesive layer is short, and damage to the dicing tape during the cleaning process can be effectively prevented. Furthermore, the composition for peeling and dissolving of the present invention contains not only a component for dissolving the adhesive layer but also a component for swelling and peeling the adhesive layer. The proportion of the dissolved component, that is, the component [I] (quaternary ammonium salt), is small, which also effectively contributes to preventing damage to the dicing tape.
When the adhesive layer removal step is performed using the peeling and dissolving composition of the present invention, damage to the dicing tape can be effectively prevented (as described in [Example 3-1] in the Examples section below). (see results).

The semiconductor substrate cleaning method of the present invention may include a step of removing the peeled adhesive layer.
The method for removing the peeled adhesive layer is not particularly limited as long as the peeled adhesive layer is removed from the top of the semiconductor substrate. The peeled adhesive layer present in the stripping and dissolving composition may be removed without taking out the semiconductor substrate from the stripping and dissolving composition. Alternatively, the peeled adhesive layer may be removed by taking out the semiconductor substrate from the peeling and dissolving composition and separating the semiconductor substrate from the peeled adhesive layer. At this time, by simply taking out the semiconductor substrate from the peeling and dissolving composition, the peeled adhesive layer may naturally remain in the peeling and dissolving composition, and most of it may be removed.

Specific examples of methods for removing the peeled adhesive layer include, for example, removing the peeled adhesive layer by adsorption or suction using a device, removing the peeled adhesive layer by blowing it away with a gas such as an air gun, or removing the peeled adhesive layer from above or below the semiconductor substrate. Examples include, but are not limited to, methods such as removing the peeled adhesive layer by centrifugal force caused by moving it left and right or rotating it.

After removing the adhesive layer peeled off from the semiconductor substrate, if necessary, the semiconductor substrate is dried or the like according to a conventional method.

(Peeling and dissolving composition)
The peeling and dissolving composition used in the semiconductor substrate cleaning method of the present invention is also an object of the present invention.
The peeling and dissolving composition of the present invention is used to remove (clean) an adhesive layer on a semiconductor substrate from the semiconductor substrate, and preferred embodiments and conditions are as described above. The stripping and dissolving composition of the present invention can be produced by mixing the solvents constituting the composition in any order if necessary. At that time, filtration etc. may be performed if necessary.

The content of the solvent represented by formula (L) in the stripping and dissolving composition of the present invention is characterized in that it is 30% by mass or more, when the aprotic solvent is 100% by mass.
In this way, in the peeling and dissolving composition, the content of component [III] (solvent represented by formula (L)), which contributes to swelling and peeling of the adhesive layer, is high. When the dissolving composition is brought into contact with the adhesive layer, swelling and peeling of the adhesive layer and dissolution of the adhesive layer are performed simultaneously.
For example, International Publication No. 2020/080060 (hereinafter referred to as Publication A) describes a method of cleaning an adhesive on a semiconductor substrate and a cleaning composition used in the cleaning method. However, the adhesive described in Publication A is not the type of adhesive that can be swollen and peeled off by a cleaning composition as the object of the present invention. Therefore, Publication A does not include the idea of swelling and peeling the adhesive layer as a means for removing the adhesive, and the cleaning composition described in Publication A removes the adhesive layer by dissolving the adhesive layer. That's all I intend. In fact, a cleaning composition was prepared using the solvent ratio described in the Examples of Publication A (see the cleaning compositions of [Comparative Examples 1-1 to 1-6] described in the Examples section below). ), it was found that the adhesive layer was not peeled off unless it contained a certain amount or more of component [III] (solvent represented by formula (L)) ([4] Peeling time described in the Examples section below) (See measurement results).
The stripping and dissolving composition of the present invention has a high content ratio of component [III] (solvent represented by formula (L)), and a high content ratio of component [II] and [III] (component [IV] If the component [II], [III] and [IV] are contained, the proportion of component [II], [III] and [IV] is high, so in the stripping and dissolving composition, component [I] (quaternary ammonium salt) is Its content is relatively small. By suppressing the content of component [I], damage to the dicing tape during the cleaning process can be reduced.

In a preferred embodiment of the stripping and dissolving composition of the present invention, the stripping and dissolving composition contains component [I], component [II], and component [III] (with or without component [IV]). In the case where the aprotic solvent is 100% by mass, the component [III] may be contained in an amount of 35% by mass or more.
In another preferred embodiment of the stripping and dissolving composition of the present invention, the stripping and dissolving composition contains component [I], component [II], and component [III] (component [IV] is When the aprotic solvent is 100% by mass, the component [III] may be contained in an amount of 40% by mass or more.
In another preferred embodiment of the stripping and dissolving composition of the present invention, the stripping and dissolving composition includes component [I], component [II], component [III], and component [IV]. , when the aprotic solvent is 100% by mass, the [III] component is 30% by mass or more, or the [IV] component is 31% by mass or less, or the [III] component is 30% by mass or more, and [IV] A composition containing 31% by mass or less of the component is exemplified.
In another preferred embodiment of the stripping and dissolving composition of the present invention, the stripping and dissolving composition includes component [I], component [II], component [III], and component [IV]. , when the aprotic solvent is 100% by mass, the [III] component is 35% by mass or more, or the [IV] component is 35% by mass or less, or the [III] component is 35% by mass or more, and [IV] A composition containing 35% by mass or less of the component is exemplified.
In particular, when the peeling and dissolving composition contains component [I], component [II], component [III], and component [IV], where component [IV] is represented by formula (G) In the case of a solvent, preferred examples include compositions containing 30% by mass or more of component [III] when 100% by mass of the aprotic solvent.
In addition, when the peeling and dissolving composition contains a [I] component, a [II] component, a [III] component, and a [IV] component, the [IV] component is represented by formula (G). In the case of a solvent, when the aprotic solvent is 100% by mass, component [III] is 30% by mass or more, or component [IV] is 35% by mass or less, or 31% by mass or less, or 30% by mass or less. Preferred examples include compositions containing the following.
Alternatively, the peeling and dissolving composition contains component [I], component [II], component [III], and component [IV], where component [IV] is represented by formula (G). In the case of a solvent, when the aprotic solvent is 100% by mass, the [III] component is 30% by mass or more, and the [IV] component is 35% by mass or less, or 31% by mass or less, or 30% by mass or less. Preferred examples include compositions containing the following.

(Method for manufacturing processed semiconductor substrate)
By using the method for cleaning a semiconductor substrate of the present invention described above, the adhesive layer on the substrate of the semiconductor substrate, in particular, the hardening obtained from the siloxane adhesive containing the polyorganosiloxane component (A') that hardens by a hydrosilylation reaction. It becomes possible to efficiently remove the adhesive layer, which is a film, and it is expected that highly efficient and good semiconductor devices can be manufactured.

In the method for manufacturing a processed semiconductor substrate of the present invention, for example, after a semiconductor wafer is polished and thinned, a support is separated (peeled off) from the processed thinned semiconductor wafer, and then the semiconductor wafer side is By removing (cleaning) the remaining adhesive layer using the semiconductor substrate cleaning method of the present invention, a processed semiconductor substrate with a clean surface without any remaining adhesive layer can be manufactured.
As described above, an example of the use of the method for cleaning a semiconductor substrate of the present invention in a semiconductor process includes use in a method for manufacturing a processed semiconductor substrate such as thinning used in semiconductor packaging technology such as TSV.

Semiconductor substrates to be cleaned in the cleaning method of the present invention include silicon semiconductor substrates such as the silicon wafers mentioned above, as well as germanium substrates, gallium-arsenide substrates, gallium-phosphorus substrates, gallium-arsenide-aluminum substrates, and aluminum plated substrates. Silicon substrate, copper-plated silicon substrate, silver-plated silicon substrate, gold-plated silicon substrate, titanium-plated silicon substrate, silicon nitride film-formed silicon substrate, silicon oxide film-formed silicon substrate, polyimide film-formed silicon substrate, glass substrate, quartz substrate, liquid crystal substrate , and various substrates such as organic EL substrates.

As a preferred embodiment of the method for manufacturing a processed semiconductor substrate of the present invention,
First step: manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition,
Second step: Processing the semiconductor substrate of the obtained laminate,
3rd step: separating the semiconductor substrate and the adhesive layer from the support substrate, and 4th step: removing the adhesive layer on the semiconductor substrate by peeling and dissolving it using a peeling and dissolving composition. Examples include a method for manufacturing a processed semiconductor substrate.
Here, the composition for peeling and dissolving is as described in the section of <Peeling and dissolving composition> above.
In the fourth step, the semiconductor substrate cleaning method of the present invention is used.
Each step will be explained in detail below.

<First step>
As the adhesive composition used to form the adhesive layer in the first step, the various adhesives mentioned above can be used, but the semiconductor substrate cleaning method of the present invention uses an adhesive composition obtained from a polysiloxane adhesive. It is effective for removing adhesive layers obtained from polysiloxane adhesives containing component (A) that cures by a hydrosilylation reaction.
Therefore, an example in which the adhesive layer is removed by the cleaning method of the present invention when manufacturing a semiconductor substrate processed using an adhesive layer obtained using a polysiloxane adhesive (adhesive composition) will be described below. However, the present invention is not limited thereto.

The first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition will be described below.

In one embodiment, the first step includes a step of applying an adhesive composition to the surface of the semiconductor substrate or the supporting substrate to form an adhesive coating layer, and a step of connecting the semiconductor substrate and the supporting substrate via the adhesive coating layer. A step of forming a laminate by applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring them into close contact with each other while performing at least one of heat treatment and depressurization treatment, and then performing post-heat treatment. including.
In other embodiments, the first step includes, for example, applying an adhesive composition to a circuit surface of a wafer of a semiconductor substrate and heating it to form an adhesive coating layer; A step of applying a release agent composition and heating it to form a release agent coating layer, and at least one of heat treatment and reduced pressure treatment of the adhesive coating layer of the semiconductor substrate and the release agent coating layer of the support substrate. while applying a load in the thickness direction of the semiconductor substrate and the support substrate to bring them into close contact with each other, and then performing post-heat treatment to form a laminate. Note that although the adhesive composition was applied to the semiconductor substrate and the release agent composition was applied to the support substrate and heated, the adhesive composition and release agent composition were applied and heated to either one of the substrates in sequence. You may go.
In each of the above embodiments, the type of adhesive composition, the specific composition of the release agent composition, and the compatibility of the film obtained from both compositions determine whether heat treatment, reduced pressure treatment, or a combination of the two is used. It is determined after taking into consideration various circumstances such as , film thickness, and desired adhesive strength.

Here, for example, the semiconductor substrate is a wafer, and the support substrate is a support body. The object to which the adhesive composition is applied may be either the semiconductor substrate or the support substrate, or both.

Examples of the wafer include, but are not limited to, silicon wafers and glass wafers with a diameter of about 300 mm and a thickness of about 770 μm.
In particular, the semiconductor substrate cleaning method of the present invention can effectively clean a semiconductor substrate with bumps.
Specific examples of such bumped semiconductor substrates include silicon wafers having bumps such as ball bumps, printed bumps, stud bumps, and plated bumps, and usually have a bump height of about 1 to 200 μm and a bump diameter of 1 to 200 μm. , a bump pitch of 1 to 500 μm.
Specific examples of plated bumps include, but are not limited to, Sn-based alloy plating such as SnAg bumps, SnBi bumps, Sn bumps, and AuSn bumps.

The support (carrier) is not particularly limited, and examples include, but are not limited to, silicon wafers with a diameter of 300 mm and a thickness of about 700 μm.

Examples of the release agent composition include compositions containing a release agent component used in this type of application.

The coating method is not particularly limited, but is usually a spin coating method. Note that a method may also be adopted in which a coating film is separately formed by a spin coating method or the like and a sheet-like coating film is attached, and this is also referred to as coating or coating film.

The heating temperature of the applied adhesive composition cannot be unconditionally defined because it varies depending on the type and amount of adhesive components contained in the adhesive composition, whether or not a solvent is included, the desired thickness of the adhesive layer, etc. However, the heating time is usually 80 to 150°C and the heating time is usually 30 seconds to 5 minutes.

The heating temperature of the applied release agent composition cannot be unconditionally defined because it varies depending on the type and amount of the crosslinking agent, acid generator, acid, etc., whether a solvent is included, the desired thickness of the release layer, etc. However, from the viewpoint of realizing suitable curing, the temperature is preferably 120°C or higher, and from the viewpoint of preventing excessive curing, the temperature is preferably 260°C or lower, and the heating time is usually 1 to 10 minutes.
Heating can be performed using a hot plate, oven, or the like.

The thickness of the adhesive coating layer obtained by applying the adhesive composition and heating it is usually 5 to 500 μm.

The thickness of the release agent coated layer obtained by applying the release agent composition and heating it is usually 5 to 500 μm.

The heat treatment is usually carried out at a temperature of 20 to 150°C, taking into account the viewpoints of softening the adhesive coating layer to achieve suitable bonding with the release agent coating layer, and achieving suitable curing of the release agent coating layer. It is determined as appropriate from the range of . In particular, from the viewpoint of suppressing and avoiding excessive hardening and unnecessary deterioration of adhesive components and release agent components, the heating temperature is preferably 130°C or lower, more preferably 90°C or lower, and the heating time is determined by the adhesive ability and peelability. From the viewpoint of reliably developing, the time is usually 30 seconds or more, preferably 1 minute or more, but from the viewpoint of suppressing deterioration of the adhesive layer and other members, the time is usually 10 minutes or less, preferably 5 minutes or less.

The reduced pressure treatment may be performed by exposing the semiconductor substrate, the adhesive coating layer, and the supporting substrate, or the semiconductor substrate, the adhesive coating layer, the release agent coating layer, and the supporting substrate to an atmospheric pressure of 10 to 10,000 Pa. The time for the reduced pressure treatment is usually 1 to 30 minutes.

In a preferred embodiment of the present invention, the substrate and the coating layer or the coating layers are bonded together, preferably by reduced pressure treatment, more preferably by a combination of heat treatment and reduced pressure treatment.

The load in the thickness direction of the semiconductor substrate and the supporting substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the supporting substrate and the layer between them and can firmly adhere them, but usually It is within the range of 10 to 1000N.

The post-heating temperature is preferably 120° C. or higher from the viewpoint of obtaining a sufficient curing rate, and preferably 260° C. or lower from the viewpoint of preventing deterioration of the substrate, adhesive component, release agent component, etc. The heating time is usually 1 minute or more from the viewpoint of achieving suitable bonding of the wafers by curing, and preferably 5 minutes or more from the viewpoint of stabilizing the physical properties of the adhesive. From the viewpoint of avoiding adverse effects on the environment, the duration is usually 180 minutes or less, preferably 120 minutes or less. Heating can be performed using a hot plate, oven, or the like.
Note that one purpose of the post-heat treatment is to more suitably cure the adhesive component (S).

<Second process>
Next, a second step of processing the semiconductor substrate of the laminate obtained by the method described above will be described.
An example of processing performed on the laminate used in the present invention includes processing the back surface of the semiconductor substrate, which is opposite to the circuit surface on the front surface, and typically involves thinning the wafer by polishing the back surface of the wafer. It will be done. Using such a thinned wafer, through-silicon vias (TSV) and the like are formed, and then the thinned wafer is peeled off from the support to form a stack of wafers, which is three-dimensionally packaged. Also, before and after this, the formation of wafer backside electrodes and the like is also performed. In the thinning and TSV process of the wafer, heat of 250 to 350°C is applied while the wafer is adhered to the support, but the adhesive layer included in the laminate used in the present invention has heat resistance to that heat. There is.
For example, a wafer having a diameter of 300 mm and a thickness of about 770 μm can be reduced to a thickness of about 80 to 4 μm by polishing the back surface opposite to the circuit surface on the front surface.

<3rd process>
The third step of separating the processed semiconductor substrate, adhesive layer, and support substrate will be explained.
In the third step, the processed semiconductor substrate and adhesive layer are separated from the support substrate. At this time, if a release layer is included in the laminate, the release layer is usually removed along with the support substrate.
The processed semiconductor substrate and adhesive layer can be separated from the semiconductor substrate by peeling between the adhesive layer and the peeling layer or supporting substrate that is in contact with it. Such peeling methods include laser peeling, sharpening, etc. Examples include, but are not limited to, mechanical peeling using a piece of equipment, manual peeling, and the like.

<4th step>
Next, a fourth step of removing the adhesive layer on the processed semiconductor substrate and cleaning the processed semiconductor substrate will be described.
The fourth step is a step of removing the adhesive layer on the semiconductor substrate using the semiconductor substrate cleaning method of the present invention. Specifically, for example, the adhesive layer on the thinned substrate is removed by the cleaning method of the present invention for a short time. Remove it cleanly. The conditions at this time are as described above.

As mentioned above, simply by performing a cleaning operation using the stripping and dissolving composition of the present invention, the adhesive layer is simultaneously swollen and dissolved, so that in the fourth step, the semiconductor substrate can be removed more cleanly in a short time. The top adhesive layer can be removed.

The method for manufacturing a processed semiconductor substrate of the present invention includes the first to fourth steps described above, but may include steps other than these steps. Moreover, the above-mentioned structural elements and methodological elements related to the first to fourth steps may be changed in various ways as long as they do not depart from the gist of the present invention.

EXAMPLES Hereinafter, the contents and effects of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. The equipment used is as follows.
[Device]
(1) Stirrer A: Rotation and revolution mixer ARE-500 manufactured by Shinky Co., Ltd.
(2) Stirrer B: Mix rotor VMR-5R manufactured by As One Co., Ltd.
(3) Viscometer: Rotational viscometer TVE-22H manufactured by Toki Sangyo Co., Ltd.
(4) Optical microscope: Olympus Corporation semiconductor/FPD inspection microscope MX61L

[1] Preparation of adhesive composition 1 [Example 1]
In a 600 mL stirring container dedicated to stirrer A, 99.12 g of a p-menthane solution (concentration 80.6% by mass) of MQ resin (manufactured by Wacker Chemi) having a polysiloxane skeleton and a vinyl group as the aforementioned component (a1), The above-mentioned component (B) is a polyorganosiloxane represented by the above-mentioned formula (M1) (complex viscosity 6000 Pa·s, weight average molecular weight 642,000 (dispersity 2.6), manufactured by Wacker Chemi, trade name GENIOPLAST GUM) 22.12 g, p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.), 48.89 g, and n-decane (manufactured by Sankyo Chemical Co., Ltd.) 5.43 g were added, and the mixture was stirred for 5 minutes using stirrer A. This was repeated a total of eight times with a short break in between to obtain a mixture (I) (total stirring time of 40 minutes).
To the obtained mixture (I), 15.98 g of SiH group-containing linear polydimethylsiloxane (manufactured by Wacker Chemi) with a viscosity of 100 mPa·s was added as the above-mentioned component (a2), and 15.98 g of a linear polydimethylsiloxane containing a SiH group (manufactured by Wacker Chemi) was added as the above-mentioned component (a1) with a viscosity of 200 mPa·s. 23.35 g of vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemi) of s was added to obtain a mixture (II).
The aforementioned component (A3) was 0.31 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), and the aforementioned component (A3) was 1-ethynyl-1-cyclohexanol (Wacker Chem. 0.31 g (manufactured by Nippon Terpene Chemical Co., Ltd.) and 0.61 g of p-menthane (manufactured by Nippon Terpene Chemical Co., Ltd.) were stirred for 60 minutes using stirrer B to obtain a mixture (III).
1.23 g of the obtained mixture (III) was added to mixture (II) and stirred for 5 minutes with stirrer A to obtain mixture (IV).
0.074 g of a platinum catalyst (manufactured by Wacker Chemi) as the aforementioned component (A2) and 7.37 g of a vinyl group-containing linear polydimethylsiloxane (manufactured by Wacker Chemi) with a viscosity of 1000 mPa·s as the aforementioned component (a1) were placed in a stirrer. A was stirred for 5 minutes to obtain a mixture (V).
3.72 g of the obtained mixture (V) was added to mixture (IV) and stirred for 5 minutes with stirrer A to obtain mixture (VI).
Finally, the obtained mixture (VI) was filtered through a 300 mesh nylon filter to obtain an adhesive composition. In addition, the viscosity of the obtained adhesive composition was 2700 mPa·s.

[2] Preparation of cleaning composition [Example 2-1]
8.08 g of N-methyl-2-pyrrolidone, 8.50 g of dibutyl ether, and 2.55 g of dipropylene glycol dimethyl ether were added to 0.59 g of tetrabutylammonium fluoride trihydrate (Kanto Chemical), stirred, and washed. A composition for use was obtained.

[Example 2-2] ~ [Example 2-12], [Example 2-26], [Comparative Example 1-1] ~ [Comparative Example 1-6]
A cleaning composition was obtained in the same manner as in Example 2-1, except that the compositions were adjusted to have the compositions shown in Tables 1 to 3 (Tables 1 to 3 are also collectively referred to as Table 1, etc.).

[Example 2-13] to [Example 2-17]
Example 2-1 except that N-ethyl-2-pyrrolidone was used instead of N-methyl-2-pyrrolidone as the N-substituted amide compound of component II, and the composition was adjusted to have the composition shown in Table 1. A cleaning composition was obtained in the same manner as above.

[Example 2-18] to [Example 2-20]
Example 2-1 except that N,N-dimethylpropionamide was used instead of N-methyl-2-pyrrolidone as the N-substituted amide compound of component II, and the composition was adjusted to have the composition shown in Table 1. A cleaning composition was obtained in the same manner as above.

[Example 2-21] to [Example 2-22]
As the N-substituted amide compound of component II, 1,3-dimethyl-2-imidazolidinone was used instead of N-methyl-2-pyrrolidone, and the composition was adjusted to be as shown in Table 1. A cleaning composition was obtained in the same manner as in Example 2-1.

[Example 2-23] to [Example 2-25]
A cleaning composition was obtained in the same manner as in Example 2-1, except that butyl acetate was used instead of dipropylene glycol dimethyl ether as component IV, and the composition was adjusted to have the composition shown in Table 1.

[Comparative example 1-7]
24.70 g of N,N-dimethylpropionamide was added to 1.3 g of tetrabutylammonium fluoride trihydrate (manufactured by Kanto Kagaku) and stirred to obtain a cleaning composition.

[3] Preparation of evaluation substrate
[Manufacturing example 1]
The adhesive composition obtained in Example 1 was applied by spin coating to a 4 cm x 4 cm silicon wafer (thickness 775 μm) as a device side wafer, and heated at 110° C. for 1.5 minutes (preheating treatment). By doing so, residual solvent on the wafer was removed and a thin film having a thickness of about 40 μm was formed on the wafer, thereby obtaining a wafer with an adhesive layer.

[4] Measurement of peeling time The wafer with adhesive layer prepared in Production Example 1 was treated with each of the cleaning compositions obtained in Examples 2-1 to 2-26 and Comparative Examples 1-1 to 1-7. It was immersed in 7 mL. The time required for the adhesive layer to completely peel off from the wafer was defined as the peeling time. The results are shown in Tables 1 to 3 below.

[5] Confirmation of presence or absence of residue after peeling The wafer with adhesive layer produced in Production Example 1 was compared to the wafer with adhesive layer obtained in Examples 2-1 to 2-26 and Comparative Examples 1-1 to Comparative Examples 1-7. It was immersed in 7 mL of each cleaning composition. If the adhesive layer peeled off within 1 minute after immersion in the cleaning composition, the peeled adhesive layer was removed with tweezers. After leaving for 1 minute from the start of immersion, the substrate was washed with isopropanol and ultrapure water, and the presence or absence of residue on the substrate was confirmed using an optical microscope. The results are shown in Tables 1 to 3 below. Comparative Examples 1-1 to 1-7 did not peel off even after 300 seconds in the test [4] above, so the test [5] was not conducted (in the table, "N.A." Notation).

[6] Check for tape damage
[Example 3-1]
As a dicing tape, DU-300 (manufactured by Nitto Denko) was cut into 4 x 4 cm pieces, immersed in 7 mL of the cleaning composition solution of Example 2-1, and left for 5 minutes.The dicing tape was then diluted with isopropanol and ultrapure water. After washing, the tape surface was observed using an optical microscope. As a result, no change was observed on the tape surface before and after dipping.
In addition, similar experiments were conducted by changing the cleaning composition liquid of Example 2-1 to the cleaning composition liquids of Examples 2-2 to 2-5, but the cleaning composition liquid of Example 2-1 was Similar to the results when using the tape, no changes were observed on the tape surface before and after dipping.

[Comparative example 2-1]
As a dicing tape, DU-300 (manufactured by Nitto Denko) was cut into 4 x 4 cm pieces, immersed in 7 mL of the cleaning composition solution of Comparative Example 1-7, and left for 5 minutes.The dicing tape was then diluted with isopropanol and ultrapure water. After washing, the tape surface was observed using an optical microscope. As a result, uneven shapes were observed on the tape surface of the substrate after immersion, and tape damage was confirmed.

When a semiconductor substrate with an adhesive layer is cleaned using the peeling and dissolving composition of the present invention, the adhesive layer is removed (cleaned) from the semiconductor substrate in a short time as shown in Examples 2-1 to 2-26. I found out that it can be done. In the present invention, most of the adhesive layer can be peeled off in a short time, so even if a small amount of the adhesive layer remains after peeling, the adhesive residue can be dissolved by the dissolved components in the peeling and dissolving composition. and then cleanly removed. This is also shown by the results of Examples 2-1 to 2-26. The adhesive layer on the semiconductor substrate could be removed cleanly by simply immersing the semiconductor substrate in the composition.
That is, by using the semiconductor substrate cleaning method of the present invention, it is possible to remove (clean) the adhesive layer from the semiconductor substrate having the adhesive layer on the surface with a simple operation, in a shorter time, and more cleanly.
Further, when the semiconductor substrate cleaning method of the present invention was used, as shown in [Example 3-1], the dicing tape was not damaged in the adhesive layer removal process.

Claims (26)

A method for cleaning a semiconductor substrate, the method comprising the step of peeling and dissolving an adhesive layer on the semiconductor substrate using a peeling and dissolving composition,
The stripping and dissolving composition is
[I] Component: quaternary ammonium salt,
[II] Component: amide solvent, and
[III] Component: A method for cleaning a semiconductor substrate, comprising a solvent represented by the following formula (L).

(In the formula, L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.) 2. The method for cleaning a semiconductor substrate according to claim 1, wherein the stripping and dissolving composition further contains component [IV]: a solvent represented by the following formula (T) or the following formula (G).
(In the formula, X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is 2 or 3. X ⁴ represents an alkyl group.)
(In the formula, L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is 7 or less. ) The method for cleaning a semiconductor substrate according to claim 1, wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt. The method for cleaning a semiconductor substrate according to claim 1, wherein the amide solvent is an acid amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y).

(In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, and R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms.)

(In the formula, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰² represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)
(In the formula, R ¹⁰³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁰⁴ represents an alkylene group having 1 to 5 carbon atoms, and *1 is a bond bonded to the carbon atom in formula (Y). *2 represents the bond bonded to the nitrogen atom in formula (Y).) The method for cleaning a semiconductor substrate according to claim 1, wherein the L ¹ and L ² are the same group. The adhesive layer includes at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. The method for cleaning a semiconductor substrate according to claim 1, wherein the film is obtained using an adhesive composition containing the agent component (S). The method for cleaning a semiconductor substrate according to claim 6, wherein the adhesive component (S) includes a siloxane adhesive. 8. The method for cleaning a semiconductor substrate according to claim 7, wherein the siloxane adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction. 2. The method for cleaning a semiconductor substrate according to claim 1, wherein the step of peeling and dissolving includes the step of removing the peeled adhesive layer. A first step of manufacturing a laminate including a semiconductor substrate, a support substrate, and an adhesive layer obtained from an adhesive composition;
a second step of processing the semiconductor substrate of the obtained laminate;
A processed semiconductor comprising: a third step of separating the semiconductor substrate and the adhesive layer from the supporting substrate; and a fourth step of removing the adhesive layer on the semiconductor substrate by peeling and dissolving it using a peeling and dissolving composition. In the method for manufacturing a substrate,
The stripping and dissolving composition comprises:
[I] Component: quaternary ammonium salt,
[II] Component: amide solvent, and
[III] Component: A method for producing a processed semiconductor substrate, characterized by containing a solvent represented by the following formula (L).

(In the formula, L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.) The method for producing a processed semiconductor substrate according to claim 10, wherein the stripping and dissolving composition further contains component [IV]: a solvent represented by the following formula (T) or the following formula (G).
(In the formula, X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is 2 or 3. X ⁴ represents an alkyl group.)
(In the formula, L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is 7 or less. ) The method for manufacturing a processed semiconductor substrate according to claim 10, wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt. The method for manufacturing a processed semiconductor substrate according to claim 10, wherein the amide solvent is an acid amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y).

(In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, and R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms.)

(In the formula, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰² represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)
(In the formula, R ¹⁰³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁰⁴ represents an alkylene group having 1 to 5 carbon atoms, and *1 is a bond bonded to the carbon atom in formula (Y). *2 represents the bond bonded to the nitrogen atom in formula (Y).) The method for manufacturing a processed semiconductor substrate according to claim 10, wherein the L ¹ and L ² are the same group. The adhesive layer includes at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. The method for producing a processed semiconductor substrate according to claim 10, wherein the film is obtained using an adhesive composition containing the adhesive component (S). The method for manufacturing a processed semiconductor substrate according to claim 15, wherein the adhesive component (S) includes a siloxane adhesive. 17. The method for manufacturing a processed semiconductor substrate according to claim 16, wherein the siloxane adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction. 11. The method for manufacturing a processed semiconductor substrate according to claim 10, wherein the fourth step of peeling and dissolving and removing includes a step of removing the peeled adhesive layer. A peeling and dissolving composition used for peeling and dissolving and removing an adhesive layer on the semiconductor substrate when cleaning the semiconductor substrate, the composition comprising:
The stripping and dissolving composition is
[I] Component: quaternary ammonium salt,
[II] Component: amide solvent, and
[III] Component: Contains a solvent represented by the following formula (L),
A composition for stripping and dissolving, characterized in that the content of the component [III] in the composition for stripping and dissolving is 30% by mass or more based on 100% by mass of the aprotic solvent.

(In the formula, L ¹ and L ² each independently represent an alkyl group having 2 to 5 carbon atoms, and L ³ represents O or S.) The stripping and dissolving composition according to claim 19, further comprising component [IV]: a solvent represented by the following formula (T) or the following formula (G).
(In the formula, X ¹ and X ³ each independently represent an alkyl group or an acyl group (X ⁴ -C(=O)-), X ² represents an alkylene group, and n is 2 or 3. X ⁴ represents an alkyl group.)
(In the formula, L ¹¹ and L ¹² each independently represent an alkyl group having 1 to 6 carbon atoms, and the total number of carbon atoms in the alkyl group in L ¹¹ and in the alkyl group in L ¹² is 7 or less. ) The stripping and dissolving composition according to claim 19, wherein the quaternary ammonium salt is a halogen-containing quaternary ammonium salt. The stripping and dissolving composition according to claim 19, wherein the amide solvent is an acid amide derivative represented by the following formula (Z) or a compound represented by the following formula (Y).

(In the formula, R ⁰ represents an ethyl group, a propyl group, or an isopropyl group, and R ^A and R ^B each independently represent an alkyl group having 1 to 4 carbon atoms.)

(In the formula, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰² represents an alkylene group having 1 to 6 carbon atoms or a group represented by the following formula (Y1).)
(In the formula, R ¹⁰³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ¹⁰⁴ represents an alkylene group having 1 to 5 carbon atoms, and *1 is a bond bonded to the carbon atom in formula (Y). *2 represents the bond bonded to the nitrogen atom in formula (Y).) 20. The stripping and dissolving composition according to claim 19, wherein ^L1 and ^L2 are the same group. The adhesive layer includes at least one selected from siloxane adhesives, acrylic resin adhesives, epoxy resin adhesives, polyamide adhesives, polystyrene adhesives, polyimide adhesives, and phenolic resin adhesives. The peeling and dissolving composition according to claim 19, which is a film obtained using an adhesive composition containing the agent component (S). 25. The processed release and dissolution composition of claim 24, wherein the adhesive component (S) comprises a siloxane adhesive. The composition for peeling and dissolving according to claim 25, wherein the siloxane adhesive contains a polyorganosiloxane component (A') that is cured by a hydrosilylation reaction.